JPS63190621A - Method of removing 1,1,1-trichloroethane out of gas containing 1,1,1-trichloroethane - Google Patents
Method of removing 1,1,1-trichloroethane out of gas containing 1,1,1-trichloroethaneInfo
- Publication number
- JPS63190621A JPS63190621A JP62023358A JP2335887A JPS63190621A JP S63190621 A JPS63190621 A JP S63190621A JP 62023358 A JP62023358 A JP 62023358A JP 2335887 A JP2335887 A JP 2335887A JP S63190621 A JPS63190621 A JP S63190621A
- Authority
- JP
- Japan
- Prior art keywords
- trichloroethane
- ozone
- gas containing
- acid catalyst
- solid acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000011973 solid acid Substances 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 3
- 239000007789 gas Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 235000010575 Pueraria lobata Nutrition 0.000 description 1
- 241000219781 Pueraria montana var. lobata Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野：
本発明は！、 １．１− ）リクロロエタンを含むガス
の処理方法に関し、さらに詳しくはガス中に含まれる１
、 １．１−トリクロルエタンを分解し、この分解生成
物を吸収及び／または吸着除去することにより、１．１
．１−トリクロルエタンを夷買上含まないガスを得る方
法に関する。[Detailed description of the invention] Industrial field of application: The present invention! , 1.1-) Regarding the method for treating gas containing dichloroethane, more specifically, the treatment of 1 contained in the gas
, 1.1 by decomposing 1.1-trichloroethane and absorbing and/or adsorbing the decomposition products.
．． The present invention relates to a method for obtaining a gas that does not contain 1-trichloroethane.
従来技術：
１、１．１−トリクロロエタンは工業用溶剤として広く
使用されている。従ってそれを使用する設備等から大気
中へ漏出する機会も多いが、そのような漏出を防止しな
ければならないことは、明かである。Prior Art: 1,1,1-trichloroethane is widely used as an industrial solvent. Therefore, there are many opportunities for leakage into the atmosphere from equipment that uses it, but it is clear that such leakage must be prevented.
従来から実施されている代表的な１，１．１−４１Ｊク
ロロエタン含４】ガス処理方法は、１．１．１−トリク
ロロエタンを活性炭等の吸着剤によシ吸着し。A typical 1,1.1-41J chloroethane-containing gas treatment method that has been practiced in the past involves adsorbing 1,1.1-trichloroethane with an adsorbent such as activated carbon.
次いでそれを脱着し、回収することからなる。しかし、
ガス中に含まれる１、 １．１−トリクロロエタンが微
量であるならば、上記の如き吸着／脱着による回収より
も、分解除去した方がコスト面（殊にエネルギーコスト
面）で有利となる場合がある。It then consists of detaching and recovering it. but,
If the amount of 1,1,1-trichloroethane contained in the gas is small, it may be more advantageous in terms of cost (especially energy cost) to decompose and remove it than to recover it by adsorption/desorption as described above. be.
１、１．１− ）ジクロロエタンは大気中においては可
成ｐ安定であり、分解速度は非常に遅い。３６０〜４４
０℃では１．１−ジクロロエチレンと塩化水・素に分解
はするが、酸化分解させるにはさらに高温を必要とする
。従って、その酸化分解を促進させるために鍍金属触媒
を用いることも行われているが、それでも反応温度は３
００℃以上にする必要があり、完全に分解するにはさら
に葛湯にしなければならない。そのためこのような分解
法の操業コストは極めて高い。1,1.1-) Dichloroethane is fairly p-stable in the atmosphere, and its decomposition rate is very slow. 360-44
At 0°C, it decomposes into 1,1-dichloroethylene and hydrogen chloride/element, but an even higher temperature is required for oxidative decomposition. Therefore, a plated metal catalyst has been used to promote the oxidative decomposition, but the reaction temperature is still 3.
It needs to be heated to 00°C or higher, and it must be further made into kudzu soup to completely decompose. Therefore, the operating costs of such a decomposition method are extremely high.
発明が解決しようとする問題点：
本発明の主要な目的課題は、ガス中に含まれる１、 １
．１− ） ＋）クロロエタンを経済的にかつ効率よく
分解し、分解生成物を吸収及び／または吸着除去する方
法を提供することである。本発明の一目的は、１．１．
１− トリクロロエタンを汚染物として含む廃ガス、あ
るいは１．１．１− トリクロロエタンを不純物として
含む原料ガス流、から１．１．１− トリクロロエタン
を効率的に除去する方法を提供することである。Problems to be solved by the invention: The main objective problem of the present invention is to solve the problem of 1, 1 contained in gas.
．． 1-) +) To provide a method for economically and efficiently decomposing chloroethane and removing the decomposition products by absorption and/or adsorption. One object of the present invention is 1.1.
The object of the present invention is to provide a method for efficiently removing 1.1.1-trichloroethane from a waste gas containing 1.1.1-trichloroethane as a contaminant or from a feed gas stream containing 1.1.1-trichloroethane as an impurity.
問題点を解決するための手段：
かくして本発明の方法は、１．１．１− トリクロロエ
タンを含むガスをまず固体酸触媒と接触させ、次いでオ
ゾンによる酸化分解処理に付し、しかる後に吸収及び／
または吸着処理に付すことを特徴とする１、 １．１−
トリクロロエタンを含むガスから１、１．１− ）ジク
ロロエタンを分解除去する方法である。Means for solving the problem: The method of the present invention thus comprises: 1.1.1- A gas containing trichloroethane is first brought into contact with a solid acid catalyst, then subjected to an oxidative decomposition treatment with ozone, and then subjected to absorption and/or decomposition treatment.
or subjected to adsorption treatment 1, 1.1-
This is a method for decomposing and removing 1,1.1-) dichloroethane from a gas containing trichloroethane.
しかして、本発明の対象となるガス中の１．１．１−ト
リクロロエタン濃度は１１１１１１〜２％程度であるこ
とが望ましく、これよシ高濃度である場合は回収し再利
用する方が経済的である。しかし高濃度の１．１．１−
トリクロロエタンを含むガスに適用できない訳ではなく
種々の条件によシさらに高濃度の場合にも適用した方が
経済的に有利である場合も生ずる。Therefore, it is desirable that the concentration of 1.1.1-trichloroethane in the gas targeted by the present invention is about 111111 to 2%, and if the concentration is higher than this, it is more economical to recover and reuse it. It is. However, high concentrations of 1.1.1-
This does not mean that it cannot be applied to gases containing trichloroethane, but depending on various conditions, there may be cases where it is economically advantageous to apply it even at higher concentrations.
固体酸触媒として最も好ましいのはアルミナであり、固
体酸触媒と１．１．１−トリクロロエタンを含むガスの
接触温度は１００〜３００℃、より好ましくは１５０〜
３００℃である。温度が１００℃未満では反応が遅く、
また３００℃より高い場合は固体酸触媒であるアルミナ
の劣化が早くなり好ましくない。尚、固体酸触媒との接
触は固定床式及び流動床式のいずれでも良く、接触時間
は６０秒で充分であるが、１秒未満では不充分である。The most preferred solid acid catalyst is alumina, and the contact temperature between the solid acid catalyst and the gas containing 1.1.1-trichloroethane is 100 to 300°C, more preferably 150 to 300°C.
The temperature is 300°C. If the temperature is less than 100°C, the reaction is slow;
Further, if the temperature is higher than 300°C, the alumina, which is a solid acid catalyst, deteriorates quickly, which is not preferable. The contact with the solid acid catalyst may be carried out by either a fixed bed method or a fluidized bed method, and a contact time of 60 seconds is sufficient, but a contact time of less than 1 second is insufficient.
オゾンとの反応は５０〜１２０℃、特に５０〜９０℃で
行なうのが好ましくオゾン量は１．１． ｌ −トリク
ロロエタン１モルに対シて１／１０〜２モルの範囲であ
ることが好ましく、通常、空気又は酸素に含有させて使
用する。また接触時間は１２０秒で充分であるが、１秒
未満では未反応物が残る可能性がある。The reaction with ozone is preferably carried out at a temperature of 50 to 120°C, particularly 50 to 90°C, and the amount of ozone is 1.1. It is preferably in a range of 1/10 to 2 moles per mole of l-trichloroethane, and is usually used in air or oxygen. Further, a contact time of 120 seconds is sufficient, but if it is less than 1 second, unreacted substances may remain.
以上によシ酸化分解したガスはアルカリ水溶液、または
アルカリ固体床と接触させ生成物を吸収させるか、活性
炭等の吸着剤により吸着させることによシ除去する。吸
着処理と吸収処理とを組合せてもよい。The gas decomposed by oxidation as described above is removed by contacting with an aqueous alkali solution or an alkali solid bed to absorb the product, or by adsorbing it with an adsorbent such as activated carbon. Adsorption treatment and absorption treatment may be combined.
実施例：
以下実施例及び比較例により本発明を具体的に説明する
。Examples: The present invention will be specifically explained below with reference to Examples and Comparative Examples.
実施例１
／ｑイレソクス製反応器（内径２０ＷｒＭ、長さ４００
情）に市販の粒状アルミナ（２〜３Ｗｎ直径）６０ＴＩ
ｔｅを充填し、これを２００℃の反応温度にまでカロ熱
し、保持した。この反応器に１．２ ｖｏ１％の１．１
゜１−トリクロロエタンを含む空気を触媒との接触時間
が１０〜２０秒となる速度で導入、通過させた。この触
媒反応器から出る反応ガス流を、０．４ｇ／ｈのオゾン
と共にテフロン製反応器（内径１０龍、長さ１５００簡
）に滞留時間１０〜４０秒、反応温度８０℃で通過させ
た。次にこのオゾン酸化分解反応器からのガスを１０％
水Ｍ化ナトリウム水溶液吸収剤中に泡立て通気した。触
媒処理、オゾン処理及び吸収処理の後にそれぞれガス試
料を採取して分析した。Example 1 /q Iresox reactor (inner diameter 20WrM, length 400
commercially available granular alumina (2~3Wn diameter) 60TI
This was heated to a reaction temperature of 200° C. and maintained. In this reactor, 1.1% of 1.2 vol.
Air containing 1-trichloroethane was introduced and passed through at a rate such that the contact time with the catalyst was 10 to 20 seconds. The reaction gas stream leaving the catalytic reactor was passed through a Teflon reactor (inner diameter 10×, length 1500×) with 0.4 g/h of ozone at a residence time of 10-40 seconds and a reaction temperature of 80° C. Next, 10% of the gas from this ozone oxidation decomposition reactor
Water was bubbled into the sodium chloride aqueous absorbent. Gas samples were taken and analyzed after each of the catalytic treatment, ozonation treatment and absorption treatment.
実施例２
実施例１と同様な装置を用い、Ｑ、３ＶＯ１％の１．１
．１− トリクロロエタンを含む窒素をアルｔす触媒（
６０ｍ７りに接触時間１０〜２０秒、触媒温度２００℃
で供給し、触媒から出るガスを、０．１９／ｈの量のオ
ゾンを含む空気と、反応温度８０℃、滞留時間１０〜４
０秒で反応させ、最後に５チ水酸化ナトリウム水溶液吸
収剤に通した。Example 2 Using the same apparatus as in Example 1, 1.1% of Q, 3VO1%
．． 1- Catalyst for nitrogen containing trichloroethane (
Contact time 10-20 seconds on 60m7, catalyst temperature 200℃
The gas coming out of the catalyst was mixed with air containing ozone in an amount of 0.19/h, reaction temperature 80°C, residence time 10-4
The mixture was allowed to react for 0 seconds, and finally passed through an aqueous sodium hydroxide absorbent.
比較例１−１
実施例１の装置の触媒反応器にアルミナの代りに顆粒状
の酸化第１鉄を６０ｗｔ１を充填し、かつその装置から
オゾン反応器部分を取り除いた。このように改変した装
置に、Ｑ、５ｖｏ１％の１．１．１−トリクロロエタン
を含む空気を、触媒温度２００℃及び接触時間１０〜２
０秒で供給した。この触媒反応後のガスを５チ水酸化ナ
トリウム水溶液吸収剤による吸収処理に付した。Comparative Example 1-1 The catalytic reactor of the apparatus of Example 1 was filled with 60wt1 of granular ferrous oxide instead of alumina, and the ozone reactor portion was removed from the apparatus. Air containing Q, 5 vol.
It was supplied in 0 seconds. The gas after this catalytic reaction was subjected to an absorption treatment using an aqueous sodium hydroxide solution absorbent.
比較例１−２
比較例１−１の触媒反応器から出たガス流に０．２９／
ｈのオゾンを加え、反応温度８０℃、滞留時間２０〜４
０秒でオゾン酸化処理し、次いで５チ水酸化ナトリウム
水溶液吸収剤による吸収処理に付した。Comparative Example 1-2 0.29/
Add h of ozone, reaction temperature 80℃, residence time 20~4
It was subjected to ozone oxidation treatment for 0 seconds, and then subjected to absorption treatment with a 5-thiodium hydroxide aqueous solution absorbent.
各実施例及び比較例の結果を次表に示す。The results of each example and comparative example are shown in the following table.
Claims (1)
固体酸触媒と接触させ、次いでオゾンによる酸化分解処
理に付し、しかる後に吸収及び／または吸着処理に付す
ことを特徴とする１，１，１−トリクロロエタンを含む
ガスから１，１，１−トリクロロエタンを分解除去する
方法。 （２）固体酸触媒がアルミナである特許請求の範囲第１
項に記載の方法。 （３）触媒接触時間が１〜６０秒である特許請求の範囲
第１または２項に記載の方法。 （５）オゾンの量が１，１，１−トリクロロエタン１モ
ルに対して１／１０〜２モルの範囲内である特許請求の
範囲第１〜４項のいずれかに記載の方法。 （６）オゾンによる酸化分解温度が５０〜１２０℃であ
る特許請求の範囲第１〜５項のいずれかに記載の方法。[Claims] (1) A gas containing 1,1,1-trichloroethane is first brought into contact with a solid acid catalyst, then subjected to oxidative decomposition treatment with ozone, and then subjected to absorption and/or adsorption treatment. A method for decomposing and removing 1,1,1-trichloroethane from a gas containing 1,1,1-trichloroethane. (2) Claim 1 in which the solid acid catalyst is alumina
The method described in section. (3) The method according to claim 1 or 2, wherein the catalyst contact time is 1 to 60 seconds. (5) The method according to any one of claims 1 to 4, wherein the amount of ozone is within the range of 1/10 to 2 moles per mole of 1,1,1-trichloroethane. (6) The method according to any one of claims 1 to 5, wherein the oxidative decomposition temperature by ozone is 50 to 120°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62023358A JPS63190621A (en) | 1987-02-03 | 1987-02-03 | Method of removing 1,1,1-trichloroethane out of gas containing 1,1,1-trichloroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62023358A JPS63190621A (en) | 1987-02-03 | 1987-02-03 | Method of removing 1,1,1-trichloroethane out of gas containing 1,1,1-trichloroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63190621A true JPS63190621A (en) | 1988-08-08 |
Family
ID=12108348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62023358A Pending JPS63190621A (en) | 1987-02-03 | 1987-02-03 | Method of removing 1,1,1-trichloroethane out of gas containing 1,1,1-trichloroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63190621A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968157A (en) * | 1988-12-15 | 1990-11-06 | Nippon Seiko Kabushiki Kaisha | Bearing lubricating system |
| JPH0347516A (en) * | 1989-03-06 | 1991-02-28 | Agency Of Ind Science & Technol | Removing method for organic halide |
-
1987
- 1987-02-03 JP JP62023358A patent/JPS63190621A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968157A (en) * | 1988-12-15 | 1990-11-06 | Nippon Seiko Kabushiki Kaisha | Bearing lubricating system |
| JPH0347516A (en) * | 1989-03-06 | 1991-02-28 | Agency Of Ind Science & Technol | Removing method for organic halide |
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